Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0009—Pigments for ceramics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62625—Wet mixtures
  • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/64—Burning or sintering processes
  • C04B35/645—Pressure sintering
  • C04B35/6455—Hot isostatic pressing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/62—Metallic pigments or fillers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/66—Copper alloys, e.g. bronze
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
  • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
  • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/40—Metallic constituents or additives not added as binding phase
  • C04B2235/408—Noble metals
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
  • C04B2235/9646—Optical properties
  • C04B2235/9661—Colour
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/256—Heavy metal or aluminum or compound thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/258—Alkali metal or alkaline earth metal or compound thereof

Definitions

• the present invention relates to a part made entirely or partly of a pigmented ceramic, particularly a timepiece, jewelery or jewelry, which can be pigmented in the mass or superficially.
• the object of the invention is precisely to overcome the aforementioned handicaps, by precisely offering timepieces, jewelery or jewelry made of ceramic in the full range of desired colors, especially in the range of reds.
• the parts according to the invention which are made of ceramic pigmented in bulk or superficially, use a pigment which consists of nanoparticles based on a metal of column IB of the periodic table of elements (in short "metal IB" or an alloy thereof, coated with a silica layer, the silica being in the form of a crystalline silica.
• the metals of column IB of the periodic table of elements of the Mendeleev table, also named class 11 according to the presentation, include copper, silver and gold, which, like the alkali metals (class IA or 1 according to presentation) have a free electron on their outermost electronic layer. As a result, they can induce surface plasmon resonance effects by creating colors, especially colors between red, violet and blue, their surface plasmon resonance being in the visible spectrum. Without going into details, recall that the surface plasmon is an exponentially decreasing wave on both sides of the interface separating the metal considered from a dielectric medium. This surface plasmon has an evanescent wave character and it is he who is responsible for the observed color effects.
• the IB metal used can be solid or plated. In the latter case, the metal IB will be only the outer layer of a particle whose core is made of another metal IB, a common metal or a mineral. We can cite for example the "vermeil”, very used in jewelery and which is silver covered with gold
• alloys such as 18-carat gold (75%) and golds commonly known as “white gold” (gold and nickel alloys), “red gold” (gold alloys and gold alloys). of copper), “green gold” (gold and silver alloys), “gray gold” (gold and iron alloys), “purple gold” (gold and aluminum alloys) “yellow gold “,” rosé "or” rose “(alloys of gold, silver and copper), etc.
• this coating serves as a diffusion barrier to the metal component of the core when the nanoparticle is subjected to high temperatures. There is no more neither coalescence nor agglutination.
• the conversion of the amorphous silica into crystalline silica coating the nanoparticles before their use as a pigment is carried out by a heat treatment at a temperature of between 800 ° C. (preferably greater than 900 ° C.) and 1,400 ° C., especially between 1'100 ° C and 1'250 ° C, the treatment times then being advantageously between 30 minutes and 24 hours.
• This treatment can be carried out in air or in an inert atmosphere, under nitrogen or argon, for example.
• the phase of the silica coating the core (s) or hearts in IB metal or alkali metal is of no importance on the result obtained as long as it is crystalline, insofar as this metal remains well contained, without migration or coalescence.
• Quartz has the disadvantage of a transformation of beta-quartz into alpha-quartz around 560 ° C with a volume variation of the order of 5%, which poses practical difficulties.
• Tridymite and cristobalite are preferred, especially cristobalite, which is simpler to obtain because it requires shorter heat treatments.
• the nanoparticles serving as the pigment may be mononuclear or polynuclear, that is to say comprise a core with a metal core IB or alkali metal, or respectively one or more nuclei, all coated in a layer of crystalline silica. We will then talk about pearls or beads.
• nanoparticles refers to particles having an average diameter generally less than 100-200 nanometers, and in this case, to obtain the desired color effects, an average particle diameter of between 5 and 25 nanometers will be chosen. preferably between 10 to 15 nanometers for mononuclear nanoparticles.
• the metals of greatest interest will therefore be those of column IB, of course copper, but more particularly gold and silver for the production of parts to be luxury products.
• ceramics will of course be used a ceramic adapted to the object that is to be shaped, but an oxide such as a zirconia, an alumina, or mixtures thereof is preferred, the zirconia being interesting for their high mechanical properties. Pure zirconia ZrO 2 is slightly yellow, alumina Al 2 O 3 is white, except dense monocrystalline aluminas which are transparent. The choice of ceramic will depend on the parts to be made. Thus, in the field of horology, zirconia will be used to make boxes or watch glasses, preferably reserving alumina to other parts such as needles.
• a zirconia When we speak of "a zirconia", it must be understood that it is intended to encompass, under these designations, not only the zirconium oxide itself, but also the zirconiums in which the zirconium element has been partially replaced by another.
• metallic element such as yttrium or magnesium.
• These ceramics are known as yttria zirconia or yttria zirconia, which comprises yttrium oxide Y 2 O 3 ; respectively magnesia zirconia, which comprises magnesium oxide MgO.
• an alumina which may include other elements than aluminum, or the designation "a ceramic” which may correspond to complex compositions, these complex ceramics may be stroichiometric or not.
• the amount of pigment dispersed in the mass of the ceramic is preferably between 1 and 5%, preferably 2 to 4%, the lower values giving more pastel shades, while the higher values give more vivid shades.
• the colors can also be modulated by varying the intrinsic color of the ceramic and / or that provided by the metal constituting the core of the nanoparticles.
• the thickness of the crystallized silica coating layer is not critical to the extent that it is sufficient. It seems that a value of 3 nm is a minimum and 50 nm is a practical maximum that will obviously reach only for "large" diameters of nanoparticles, of the order of 100-200 nanometers. This thickness has relatively little effect on the color, unlike the size of the nanoparticles themselves. For example, in the case of gold, the larger the size of the nanoparticles, the more the shade fades to a metallic blue while, the smaller it is, the more the shade pulls towards the red.
• the preparation of metal nanoparticles coated with crystalline silica is carried out in suspension in an alcoholic medium (methanol, ethanol, propanol, isopronanol or isobutanol in particular) in the presence of ammonia.
• Fine colloidal particles of the selected metal are suspended in the aforementioned medium, and then added as Si source, an alkoxysilane also called alkylorthosilicate or siloxane (terms used interchangeably in the following description) whose transformation in the presence of Water added to the reaction mixture will produce silica that deposits on the metal particles. Colored metal nanoparticles coated with amorphous silica are thus obtained.
• the nanoparticles coated with amorphous silica are converted into nanoparticles coated with crystalline silica by heating them, once isolated, at the temperatures indicated above. For example, by heating gold nanoparticles at 1200 ° C in air for a few hours, gold nanoparticles are obtained, which, unexpectedly, the color saturation increases sharply. This is because the amorphous silica coating the gold has transformed into one of its crystalline phases, in this case cristobalite which is a metastable phase at room temperature.
• the colored ceramic parts are then made by sintering a powder consisting of the mixture of ceramic particles, for example zirconia, alumina or mixtures thereof, as indicated above, and nanoparticles of crystalline silica pigment.
• the sintering may take place for example at a final temperature of between 900 ° C. and 1'400 ° C. for 30 minutes to 24 hours and possibly under pressure.
• the sintering itself can be preceded by pre-sintering.
• the methods for forming ceramic parts are well known and can be grouped into categories, namely wet methods, dry methods, and injection methods. In the former, mention will be made of slip casting, strip casting and die casting or low pressure injection molding. Among the second ones, cold or hot uniaxial pressing, hot or cold isostatic pressing and flash sintering, for example, will be named. Finally, among the thirds, there will be indicated by way of example the low-pressure injection molding (already mentioned above) and the high-pressure injection molding. All are suitable in varying degrees for manufacturing the pigmented ceramic parts according to the invention.
• a nanostructured or dispersed ceramic powder, and / or comprising adjuvants will be advantageously used, and the methods of the invention will be preferred. wet.
• the manufacture of the pigmented ceramics according to the invention is ecological and environmentally friendly. It does not use other solvents than alcohols.
• Examples 1 to 7 relate to pigmentations in the mass, while Example 8 relates to surface pigmentation.
• Amorphous silica nanoparticles with a gold core are thus obtained, which are heated in air at 1200 ° C. for several hours, until a significant change in the saturation of the colour.
• the slip method is used by proceeding by filtration under pressure of a stabilized colloidal suspension containing isolated nanostructured yttria-zirconia particles and pigment nanoparticles at a rate of 2% by weight pigment / zirconia the proportion by weight of solid in the suspension may be between 10 and 60%.
• the suspension is then forced by a piston through a ceramic filter covered with a filter, at a pressure of the order of 10 MPa which remains constant until all the suspension is filtered.
• the piece was dried by desiccation until its mass stabilized, and then sintered in air at 1200 ° C to 1300 ° C. This gives a bright red ceramic piece.
• the weight proportions nanoparticles / zirconia can vary from 0.5 to 5%, subject to what is indicated in the following example.
• the filtration pressure can range from 2 to 20 MPa, and the sintering time varies from 30 minutes to 8 hours, while remaining in the red range.
• Example 2 The procedure is as described in Example 1, but after the drying operation of the native part by desiccation, it is subjected to a complementary cold isostatic pressing step. This makes it possible to densify the part even further before sintering.
• Example 2 The procedure is as described in Example 1, but after the drying operation of the native part by desiccation, the latter is subjected to a presintering step in air at a temperature between 1000 ° C. and 1 ° C. '200 ° C. The workpiece is then subjected to hot pressurized isostatic pressing and an inert gas atmosphere of 50 to 300 MPa at a temperature of between 1200 ° C and 1300 ° C.
• Example 2 The procedure is as described in Example 1, but with higher nanoparticles / zirconia weight proportions (4%). As the particles then tend to agglomerate, this tendency is countered by subjecting the mixture to ultrasonic dispersion treatment.
• Example 1 The procedure is as described in Example 1, replacing the suspension of gold with a suspension of silver, and thus obtaining a piece pigmented with silver nanoparticles, in a shade of red more yellow than the piece of the example 1.
• Example 1 The procedure is as described in Example 1, replacing the zirconia with alumina, and thus obtaining a piece whose red draws on the rose, when compared to the piece of Example 1.
• Example 2 The procedure is as described in Example 1, replacing the zirconia with a zirconia / alumina mixture of 50/50 by weight, and thus a red piece is obtained.
• the ethanol and the tetraethylorthosilicate can be replaced by another alcohol and another tetraalkyllorthosilicate, preferably using the same R Alkyl residue, for example by using TMOS tetramethylorthosilicate if methanol is used as the alcohol or the alcohol. tetraisopropylorthosilicate if isopropanol etc. is used.

Priority Applications (7)

Applications Claiming Priority (1)

Publications (2)

Family

ID=37395945

Family Applications (1)

Country Status (6)

Families Citing this family (23)

Family Cites Families (8)

• 2006
  • 2006-07-31 DE DE06405325T patent/DE06405325T1/de active Pending
  • 2006-07-31 DE DE602006009921T patent/DE602006009921D1/de active Active
  • 2006-07-31 EP EP06405325A patent/EP1887052B1/fr active Active
• 2007
  • 2007-07-27 CN CN2007101391943A patent/CN101116910B/zh active Active
  • 2007-07-31 JP JP2007198836A patent/JP5467713B2/ja active Active
  • 2007-07-31 US US11/831,245 patent/US7897253B2/en active Active
• 2008
  • 2008-08-05 HK HK08108644.5A patent/HK1119443A1/xx unknown

Also Published As

Similar Documents

Legal Events